Insoluble azodyestuffs



Patented Mar. 16, 1937 Eugene Markush, Jersey City, N. .L, assignor toPharma Chemical Corporation, New York, N. Y'., a corporation of NewYork.

No Drawing. Application August 25, 1933, Serial 4 Claims. (01. 2 -54 Myinvention relates to coloring matters, or'

dyes, andflrefers particularly to compounds of this generalclassiiication adaptable for coloring or dyeing cellulose fibers.

I have found that valuable compounds suitable for the coloring, ordyeing of cellulose fibers can be produced by combining the diazotizedproduct of compounds having the general formula.

I HN-oox (in which and Y" are the same or different alkyl'or arylgroups, and X is a hydrocyclic or stance employing a diazotized compoundand a coupling component. I

A mixture of 85 parts 2.5 diethoxyl-iuroylamino --benzol-1-diazo-imino-'proline' and 6.9 parts. B-hydroxy-naphthoic+acideorthotoluidide ispasted up with 500 parts of water and 18 parts of sodium hydrate 80 B.The mixture is thoroughly stirred and heated to 40 C. until a clearsolution results. Acetic or formic acid is added slowly until thesolution shows excess of acid and the heating continued. A greenish blueprecipitate separates out. The temperature is mamtained at 80-90 (2.,until no further dye is formed. The dye is filtered, washed thoroughlyand dried. The bright blue pigment obtained has excellent properties;Its formula is probably:

on on 1 1 Z OiHr- 0H Nn-oo on OANHQ CH:

heterocyclic residue) with acoupling component, such as the arylides ofbeta-hydroxy-naphthoic acid. 1

The compounds of my invention may be produced in substance or upon thecellulose fiber.

In producing the compounds of my invention, in substance, thediazotized, compound is combined with the coupling component, while inproducing themupon the fiber, the fiber may be first treatedorimpregnated, with the coupling component and, thediazotized compoundapplied thereto, or the fiber treated or impregnated with the couplingcomponent may be converted into'my-new'compound by the application, of astabilized compound-of the diazotized product and then subjected toanacid treatment, or the stabilized compound of the diazotized product maybe. mixed with the coupling component and this mixture applied to thefiber and. developed thereon by anacid treatment.

I give the following as an example of the pro-. duction ofa compound oimyinvention in sub:

lllWWWm 11willllllllllum\\mutt...

I give the following as an example of the-production of a compound of myinvention in sub stance employing a stabilized diazotized compound and acoupling component.

Example 2 I Example 3 8.5 parts of 2:5 diethoxy 4-furoylaminobenzol-l-diazo iminorproline furoylamine-amino- 10 manner.

CHI.

with acetic acid for 3-50 minutes or by immersing in a hot bathcontaining salt and acetic or formic acid, until maximum intensity isreached. The developed material is then soaped hot, rinsed well anddried. A beautiful brilliant greenishblue is obtained.

The color can be also obtained on the fibre by using the padding method,the material being 30 padded with 100 parts beta-hydroxy-naphthoic- 0may be printed on by thickening with starchacid-ortho-toluidide in theusual manner.

The diazonium is prepared by pasting up 33 CIHIO parts 2.5 diethoxy4-furoylamino-aniline-hydrochloride in 200 parts of Water and 20 partshydrochloric acid 20 B. 0001 to 5 C. by means of ice and add slowly asolution of '7 parts sodium nitrite .dissolved in 35 cc. of water. Thegreenish yellow diazonium solution; when finished is then neutralizedwith sodium acetate. If the padded material is cloth, the diazoniumtragacanth. Padded cloth or hank may be developed in the usual immersionmethod. Only one-half of the diazonium solution is necessary for'the.padded material. After printing or im- 55 mersing with the diazonium thecloth is aged,

soaped, rinsed and dried.

I give the following as further examples of the production of compoundsof my invention.

Example 4 parts of the diazo amino compound obtained by combining inalkaline solution the diazonium of 2:5 dimethoxy-l-alpha-pyrollidone-(alphacarbonylamino) -aniline of the formula,

CHI\ Nance; on, oo

with hydroxy-proline subsequently salted, fil- CHiO tered, and dried aremixed with 8 parts betahydroxy-naphthoic-acid-anilide. The mixture iftreated and printed as previously described, yields a bright reddishblue of excellent properties.

This mixture may be used also to obtain the dye in substance when thesolution is treated with acetic or formic acid as previously described.The pigment is a brilliant reddish-blue powder with excellentproperties. Its probable formula 1s:

O OH:

H lam- 3 As in Example 3 the dye may also be prepared by combining thediazonium solution with the coupling, component or on the goods by thedia zonium and the padded material in the manner previously mentioned. V

I give, the following as further examples of the production of compoundsof my invention.

Example '5 In a similar manner a clear blue shade of the dye whoseprobable formula is: i

NH.O 0-0 H is obtained by treating, as above a mixture of 9 parts 2:5diethoxy-4 cyclohexyl-carbonyl-aminobenzene-l-diazoimino-proline and 7parts betahydroxy-naphthoic-acid-ortho-toluldide.

Or diazotizing a molecular proportion of the 2:5 diethoxy4-cyclohexyl-carbonylamino-anlline and combining it in organic acidmedium with a molecular proportion ofbeta-hydroxynaphthoic-acid-ortho-toluidide either in substance or on thepadded fibre.

Example 6 10 parts of the diazo amino compound obtained by combining inalkaline solution the diazonium of2-methoxy-5-ethoxy-4-alpha-pyrollidone- (alpha-carbonyl-amino) -anilineof the formula,

OCH:

with hydroxy-proline, subsequently salted, filtered and dried, are mixedwith 8 parts beta-oxy-naphthoic-acid-anilid. The mixture if treated andprinted as previously described, yields a bright marine blue ofexcellent properties.

This mixture may be used also to obtain the dye in substance when thesolution is treated with acetic or formic acid as previously described.The pigment is a brilliant marine blue powder with excellent properties.Its probable formula I do not limit myself to the particular times, is:temperatures, quantities, compounds, formulaeor OCH: OH

clm-o- CONH- on, on, NH-oo-oH c0 N{ Example 7 steps of procedurespecifically mentioned, as these are given simply as a means for clearlydescribing my invention.

What I claim is:-

1. The process of producing water-insolublecompounds which comprisescombining diazotized 2:5 methoxy-l-furoylamine-amino-benzol withbeta-hydroxy-naphthoic acid ortho-toluidide.

100 grams of material (cotton cloth or yarn) are padded with grams ofbeta-oxy-naphthoic- 15 acid-ortho-toluidide in the usual manner. The sotreated or impregnated, material is then placed into a bath containingabout 8 grams of Z-ethoxy- 5-phenyl-oxy-l-alpha-pyrollidone (alphacarbo-nylamino) -aniline.

After the dye is fully developed, the material is A oo po i of matterhaving the formula! 0 CaHs 1|?CfilH HO C-CONH N==N washed in a boilingsoap bath, a clear blue dyeing in which X is a member of the groupconsisting of is thus obtained. The probable formula of the H, CH3, orOCHs, and. which compound is of a dye is: bluish color and is insolublein water.

OOH! OH H O-NH- c, -o CHr-CH| c O NH-CO.-CH 00 Without limiting myselfto the specified com- 3. A compound having the formula 001E: OH

H olnlo- 1 00-3? -c I; GO \/OH I 7 Ha pounds, I mention the following asamong the 5 diazotizable amines and coupling components which can beemployed in the production of the compounds of my invention:

which compound is insoluble in water and is of a bluish color.

4. A compound producible by combining diazotized 2:5dimethoxy-4-furoylamine-amino-benzol with beta-hydroxy-naphthoic acidortho-tolui- Diazotized amine omplmg Shade dlde havmg the formulacomponent 2-5111lD0-4-111Bthyl-5-fl1l0yl- 2,3-hydroxy-naph- Clear violetI I amido-methoxy-benzol thorc acid-orthoanisidide 0011, OH4amino-3-6-diphenoxy iuroyl 2,3-hydroxy-naph- Bright greenamido-benzolthoic acid-ortholSh blue 6 toluidide 0H H N 4amino-3-6 -d1methoxy thi-2,3-hydroxy-naph- Reddishblue (3 H ophene-alpha-carboxythoic acid-o-aniyamido-benzol sidide I Nnco-c H, 1-amino-2-5-dimethoxy 4-2,3-hydroxy-naph- Clear-reddish H CH pyrollidine-alpha carboxythoicacid-anilido blue 0 amido-benzol l-amino-Z-fi-diethoxy-l-hexa-2,3-hydroxy-naph- Clear blue CH hydro-carboxy-amido-benzol 211101551s(a.icid-orthoo m 1 e which compound is insoluble in water and is of aIt will thus be seen that the compounds of my bluish color. inventionpossess valuable coloring or dyeing 5 properties. EUGENE A. MARKUSH.

